Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

Trimethyltin fluoride (Me3SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes {(1,2,4‐tBu3C5H2)2ThF2, (C5Me5)2U(F)(O‐2,6‐iPr2C6H3), U(F)(O‐2,6‐tBu2C6H3)3, U(F)[N(SiMe3)2]3, (C5Me5)2UF2(L) (L = O=PMe3, O=PPh3, O=PCy3), and (C5Me5)2U(F)(=N‐2,6‐iPr2C6H3)} from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C5Me5)2UF2(L) (L = O=PPh3, O=PCy3) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X‐ray crystallography. Trimethyltin fluoride (Me3SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium and uranium from their corresponding chloride, bromide, and iodide analogues.